甲醇/二甲醚制烯烃催化剂改性的研究进展  

Research progress on catalyst modification for methanol/dimethyl ether to olefins

作　　者：刘应慧 王鸿晶 王晓胜[1] 李然家[1] 余长春[1] 杨鹏程 LIU Yinghui;WANG Hongjing;WANG Xiaosheng;LI Ranjia;YU Changchun;YANG Pengcheng(College of New Energy and Materials,China University of Petroleum(Beijing),Beijing 102249,China;Shandong Hi-tech Spring Material Technology Co.,Ltd.,Dongying 257000,Shandong,China)

机构地区：[1]中国石油大学(北京)新能源与材料学院,北京102249 [2]山东海科新源材料科技股份有限公司,山东东营257000

出　　处：《低碳化学与化工》2024年第6期24-34,共11页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22008260);中国石油大学(北京)科研基金(2462021YJRC011)。

摘　　要：甲醇制烯烃(MTO)工艺已经在工业中得到广泛应用,但此工艺使用的分子筛催化剂还存在丁烯、丁烷等C_(4+)产物选择性偏高和分子筛催化剂易积碳失活的问题。因此,有必要进一步探索提高低碳烯烃选择性和抑制催化剂积碳过程的方案。综述了ZSM-5和SAPO-34的晶粒尺寸调节、孔道调节和酸性质调控的研究进展,以及分子筛催化剂体系内的二甲醚制烯烃(DTO)反应特征,总结了烃池机理中的烯烃反应机理,简述了丝光沸石(MOR)在MTO、DTO反应体系中的研发潜力,如MOR有望进一步调节低碳烯烃在产物中的比例。MTO、DTO的反应机理尚未得出定论,目前的催化剂改性方案能小幅度提升低碳烯烃的产物选择性并利用介微孔结构延缓积碳。今后,构建复合型催化剂是解决工业化中低乙烯和丙烯选择性比和易积碳问题的直接方案。Methanol to olefins(MTO)process is widely used in industry,but the molecular sieve catalysts used in the process still have some issues,such as high selectivity of C_(4+)products(butene,butane,etc.)and easy carbon deposition and deactivation.Therefore,it is necessary to further explore methods to enhance the selectivity of low carbon olefins and inhibit carbon deposition.The research progress on grain size regulation,pore regulation and acid property regulation of ZSM-5 and SAPO-34,and the reaction characteristics of dimethyl ether to olefins(DTO)in molecular sieve system were reviewed.The olefins formation mechanism in the hydrocarbon pool mechanism was summarized,and the potential of using mordenite(MOR)in MTO and DTO reaction systems was briefly discussed,such as its potential to further regulate the distribution of low carbon olefins in the final products,and it is anticipated that this can help regulate the distribution of low carbon olefins in the final products.The reaction mechanisms for MTO and DTO reactions remain undetermined,and current catalyst modification schemes can provide slight improvements in product selectivity of low carbon olefins and delay carbon deposition by mesoporous structures.In the future,building composite catalysts is a direct solution to solve the problems of low selectivity ratio of ethylene and propylene and easy carbon deposition in industrialization.

关 键 词：甲醇 二甲醚 烯烃 催化剂改性 ZSM-5 SAPO-34 

分 类 号：TQ221.2[化学工程—有机化工]